Hydrogen-Bonding Activation of Gold(I) Chloride Complexes: Enantioselective Synthesis of 3(2H)-Furanones by a Cycloisomerization-Addition Cascade.

Enantioselective synthesis of 3(2H)-furanones has been achieved using the intermolecular H-bonding activation of gold(I) chloride complexes. A DM-BINAP [(R)-(+)-2,2'-Bis[di(3,5-xylyl)phoshino]-1,1'-binaphthyl] digold(I) dichloride complex in combination with a sulfonyl squaramide (SO2Sq) has been identified as the optimal catalytic system. The process involves a 5-endo-dig oxa-cyclization followed by stereocontrolled addition of indoles. Interestingly, the soft L*Au-Cl activation by H-bonding allowed the recovery of both L*Au-Cl and the activator after chromatographic purification.

Altered activation of the dorsal anterior cingulate cortex during oddball performance in individuals at risk for Alzheimer's disease.

INTRODUCTION: The neural mechanisms underlying neurodegenerative disorders in the elderly remain elusive, despite extensive neuroimaging research in recent decades. Amnestic type mild cognitive impairment (aMCI) and late-life major depressive disorder (MDD) are two such conditions characterized by intersecting cognitive and affective symptomatology, and they are at a higher risk for Alzheimer's disease. MATERIALS AND METHODS: This study analyzed the neural underpinnings of cognitive and depressive symptoms in a cohort comprising 12 aMCI subjects, 24 late-life MDD patients, and 26 healthy controls (HCs). Participants underwent a detailed neuropsychological assessment and completed a visual attentional oddball task during functional magnetic resonance imaging (fMRI), with evaluations at baseline and at 2-year follow-up. RESULTS: Initial findings showed that aMCI subjects had reduced dACC activation during oddball (target) stimulus detection, a pattern that persisted in longitudinal analyses and correlated with cognitive functioning measures. For HCs, subsequent dACC activation was linked to depression scores. Furthermore, in the affective-cognitive altered groups, later dACC activation correlated with oddball and memory performance. CONCLUSIONS: These findings enhance our comprehension of the neurobiological basis of cognitive and depressive disturbances in aging, indicating that dACC activation in response to a visual attentional oddball task could serve as a neural marker for assessing cognitive impairment and depression in conditions predisposing to Alzheimer's disease.

Structural heart transcatheter interventions in orthotopic cardiac transplant and left ventricular assist devices recipients: A nationwide study.

BACKGROUND: The current incidence and outcomes of structural transcatheter procedures in heart transplant (HTx) recipients and left-ventricular assist devices (LVAD) carriers is unknown. AIMS: To provide insights on structural transcatheter procedures performed across HTx and LVAD patients in Spain. METHODS: Multicenter, ambispective, observational nationwide registry. RESULTS: Until May/2023, 36 percutaneous structural interventions were performed (78% for HTx and 22% for LVAD) widely varying among centers (0%-1.4% and 0%-25%, respectively). Percutaneous mitral transcatheter edge-to-edge (TEER) was the most common (n = 12, 33.3%), followed by trancatheter aortic valve replacement (n = 11, 30.5%), and tricuspid procedures (n = 9, 25%). Mitral TEER resulted in mild residual mitral regurgitation in all but one case, mean gradient was <5 mmHg in 75% of them at 1-year, with no mortality and 8.3% re-admission rate. Tricuspid TEER resulted in 100% none/mild residual regurgitation with a 1-year mortality and readmission rates of 22% and 28.5%, respectively. Finally, trancatheter aortic valve replacement procedures (n = 8 in LVADs due to aortic regurgitation and n = 3 in HTx), were successful in all cases with one prosthesis degeneration leading to severe aortic regurgitation at 1-year, 18.2% mortality rate and no re-admissions. Globally, major bleeding rates were 7.9% and 12.5%, thromboembolic events 3.7% and 12.5%, readmissions 37% and 25%, and mortality 22% and 25%, in HTx and LVADs respectively. No death was related to the implanted transcatheter device. CONCLUSIONS: Most centers with HTx/LVAD programs perform structural percutaneous procedures but with very inconsistent incidence. They were associated with good safety and efficacy, but larger studies are required to provide formal recommendations.

Understanding factors impacting patient-reported outcome measures integration in routine clinical practice: an umbrella review.

PURPOSE: Patient-report outcome measures (PROMs) have gained widespread support as a mechanism to improve healthcare quality. We aimed to map out key enablers and barriers influencing PROMs implementation strategies in routine clinical practice. METHODS: An umbrella review was conducted to identify reviews exploring enablers and barriers related to the integration of PROMs in routine clinical practice from January 2000 to June 2023. Information on key enablers and barriers was extracted and summarised thematically according to the Theoretical Domains Framework. RESULTS: 34 reviews met our criteria for inclusion. Identified reviews highlighted barriers such as limited PROMs awareness among clinicians and patients, perceived low value by clinicians and patients, PROMs that were too complex or difficult for patients to complete, poor usability of PROMs systems, delayed feedback of PROMs data, clinician concerns related to use of PROMs as a performance management tool, patient concerns regarding privacy and security, and resource constraints. Enablers encompassed phased implementation, professional training, stakeholder engagement prior to implementation, clear strategies and goals, 'change champions' to support PROMs implementation, systems to respond to issues raised by PROMs, and integration into patient pathways. No consensus favoured paper or electronic PROMs, yet offering both options to mitigate digital literacy bias and integrating PROMs into electronic health records emerged as important facilitators. CONCLUSIONS: The sustainable implementation of PROMs is a complex process that requires multicomponent organisational strategies covering training and guidance, necessary time and resources, roles and responsibilities, and consultation with patients and clinicians.

Seeking Efficiency for the Accurate Draping of Digital Garments in Production.

Digital garments are set to revolutionize the apparel industry in the way we design, produce, market, sell and try-on real garments. But for digital garments to play a central role, from designer to consumer, they must be a faithful digital replica of their real counterpart: a digital twin. Yet, most industry-grade tools used in the apparel industry do not focus on accuracy, but rather on producing fast and plausible drapes for interactive editing and quick feedback, thus limiting the value and the potential of digital garments. The key to accuracy lies in using the proper underlying simulation technology, well documented in the academic literature but historically sidelined in the apparel industry in favor of simulation speed. In this paper, we describe our industry-grade cloth simulation engine, built with a strong focus on accuracy rather than sheer speed. Using a global integration scheme and adopting state of the art simulation practices from the Computer Graphics field, we evaluate a wide range of algorithms to improve its convergence and overall performance. We provide qualitative and quantitative insights on the cost and capabilities of each of these features, with the aim of giving valuable feedback and useful guidelines to practitioners seeking to implement an accurate and robust draping simulator.

Topological and spectral properties of random digraphs.

We investigate some topological and spectral properties of Erdos-Rényi (ER) random digraphs of size n and connection probability p, D(n,p). In terms of topological properties, our primary focus lies in analyzing the number of nonisolated vertices V_{x}(D) as well as two vertex-degree-based topological indices: the Randic index R(D) and sum-connectivity index χ(D). First, by performing a scaling analysis, we show that the average degree 〈k〉 serves as a scaling parameter for the average values of V_{x}(D), R(D), and χ(D). Then, we also state expressions relating the number of arcs, largest eigenvalue, and closed walks of length 2 to (n,p), the parameters of ER random digraphs. Concerning spectral properties, we observe that the eigenvalue distribution converges to a circle of radius sqrt[np(1-p)]. Subsequently, we compute six different invariants related to the eigenvalues of D(n,p) and observe that these quantities also scale with sqrt[np(1-p)]. Additionally, we reformulate a set of bounds previously reported in the literature for these invariants as a function (n,p). Finally, we phenomenologically state relations between invariants that allow us to extend previously known bounds.

Blood flow restriction as a post-exercise recovery strategy: A systematic review of the current status of the literature.

The aim of this study was to systematically review the current literature on blood flow restriction (BFR) as a post-exercise recovery strategy. Experimental studies investigating the effect of BFR on recovery after exercise were included. Only studies meeting the following inclusion criteria were selected: (a) studies investigating about BFR as a post-exercise recovery strategy in athletes and healthy individuals; (b) the full text being available in English; (c) experimental research study design. Studies that exclusively analyzed BFR as a recovery strategy during the exercise (e.g., recovery strategy between bouts of exercise) were excluded. A literature review was conducted on the PubMed, Cochrane, and Web of Science electronic databases up until May 7th, 2023. The main findings were that (i) 9 studies investigated passive BFR as a post-exercise recovery strategy, which shows a significant lack of research in both team and individual sports (especially in female populations), and only 2 studies used active BFR protocols; (ii) although a high quality range of studies was observed, there were methodological limitations such as BFR interventions that were usually conducted after fatiguing protocols or fitness tests, which may not represent the real exercise (e.g., a sprint session of 6 sets of 50 m may induce muscle damage but it does not represent the demands of a team sport like rugby or soccer); (iii) there is a lack of consistency in BFR protocols (e.g., number of cycles or duration of the occlusion-reperfusion periods) for recovery; (iv) some studies showed beneficial effects while others found no positive or detrimental effects of BFR as a post-exercise recovery strategy in comparison with the control/SHAM group. In conclusion, only 11 studies investigated BFR as a post-exercise recovery strategy and there is not any significant amount of evidence in team or individual sports (especially in female populations). BFR could be a potential post-exercise recovery strategy, but practitioners should use caution when applying this method of recovery for their athletes and clients. In addition, it would be of interest for high performance-related practitioners to have a better understanding of the benefits of BFR interventions combined with either active or passive forms of exercise as a post-exercise recovery strategy.

Exploring the midgut physiology of the non-haematophagous mosquito Toxorhynchites theobaldi.

Toxorhynchites mosquitoes have an exclusively phytophagous feeding habit as adults, which leads to significant differences in their morphophysiology compared with haematophagous mosquitoes. However, the molecular mechanisms of digestion in this mosquito are not well understood. In this study, RNA sequencing of the posterior midgut (PMG) of the mosquito Toxorhynchites theobaldi was undertaken, highlighting its significance in mosquito digestion. Subsequently, a comparison was made between the differential gene expression of the PMG and that of the anterior midgut. It was found that the most abundant proteases in the PMG were trypsin and chymotrypsin, and the level of gene expression for enzymes essential for digestion (such as serine protease, α-amylase and pancreatic triacylglycerol lipase) and innate immune response (including catalase, cecropin-A2 and superoxide dismutase) was like that of haematophagous mosquitoes. Peritrophin-1 was detected in the entire midgut, with an elevated expression level in the PMG. Based on our findings, it is hypothesized that a non-haematophagic habit might have been exhibited by the ancestor of Tx. theobaldi, and this trait may have been retained. This study represents a pioneering investigation at the molecular level of midgut contents in a non-haematophagous mosquito. The findings offer valuable insights into the evolutionary aspects of feeding habits in culicids.

Burnout, Engagement, and Resilience During the COVID-19 Lockdown: Keys to a Model for Teachers' Self-Efficacy.

BACKGROUND: Social isolation measures by the COVID-19 pandemic have impacted teaching work. In an "Emergency Remote Teaching" (ERT) context, it is relevant to investigate the factors that affect teachers' self-efficacy. METHODS: A total of 289 teachers from schools in southern Spain have participated in this study. They have been asked about their levels of burnout, engagement, and resilience. Comparisons were made by groups in accordance with sex, type of center they belonged to, school social context, and educational level in which the teacher taught. Using a Structural Equations Model, the multivariate relationships between the variables related to burnout, engagement, and resilience were described. RESULTS: During the ERT, teachers' self-efficacy was influenced by the 3 factors: burnout-exhaustion and cynicism-engagement, and resilience. During the ERT, the teachers in semi-private and private centers showed greater self-efficacy. In turn, the teachers in childhood and primary education showed a significantly higher level of work engagement than the teachers in compulsory and post-compulsory secondary education. CONCLUSIONS: The results in relation to ERT are discussed in the context of the exceptionality and universal globality of the pandemic phenomenon and the complex self-perception of the social value of the teaching function.

STUB1 Mutations as Possible Genetic Modifiers in Spinocerebellar Ataxia Type 8.

BACKGROUND: Spinocerebellar ataxia type 8 (SCA8) is a dominantly inherited expansion disorder with highly variable penetrance. ATXN8OS/ATXN8 expanded alleles have been identified in association with other types of hereditary ataxias, pointing to a possible genetic synergism. OBJECTIVES: We aimed to further investigate the molecular background of patients with SCA8 diagnosis. METHODS: Patients were selected from our cohort of 346 families. A total of 14 probands with SCA8 underwent additional investigation through exome sequencing. RESULTS: Pathogenic heterozygous STUB1 variants were found in 21.4% of SCA8 patients (3 of 14) compared to only 0.5% in the non-SCA8 group (1 of 222), indicating a statistically significant association (P < 0.05). CONCLUSIONS: The findings reported in this study might suggest a genetic synergism between STUB1 and ATXN8OS/ATXN8 expanded alleles. Further studies are needed to validate this observation and better define the clinical impact of this genetic interaction. © 2024 The Author(s). Movement Disorders published by Wiley Periodicals LLC on behalf of International Parkinson and Movement Disorder Society.

Dynamic changes in mRNA nucleocytoplasmic localization in the nitrate response of Arabidopsis roots.

Nitrate is a nutrient and signal that regulates gene expression. The nitrate response has been extensively characterized at the organism, organ, and cell-type-specific levels, but intracellular mRNA dynamics remain unexplored. To characterize nuclear and cytoplasmic transcriptome dynamics in response to nitrate, we performed a time-course expression analysis after nitrate treatment in isolated nuclei, cytoplasm, and whole roots. We identified 402 differentially localized transcripts (DLTs) in response to nitrate treatment. Induced DLT genes showed rapid and transient recruitment of the RNA polymerase II, together with an increase in the mRNA turnover rates. DLTs code for genes involved in metabolic processes, localization, and response to stimulus indicating DLTs include genes with relevant functions for the nitrate response that have not been previously identified. Using single-molecule RNA FISH, we observed early nuclear accumulation of the NITRATE REDUCTASE 1 (NIA1) transcripts in their transcription sites. We found that transcription of NIA1, a gene showing delayed cytoplasmic accumulation, is rapidly and transiently activated; however, its transcripts become unstable when they reach the cytoplasm. Our study reveals the dynamic localization of mRNAs between the nucleus and cytoplasm as an emerging feature in the temporal control of gene expression in response to nitrate treatment in Arabidopsis roots.

Eco-geographic and sexual variation of the ribcage in Homo sapiens.

Up to now, Allen and Bergmann's rules have been studied in modern humans by analyzing differences in limb length, height, or body mass. However, there are no publications studying the effects of latitude in the 3D configuration of the ribcage. To assess this issue, we digitally reconstructed the ribcages of a balanced sample of 109 adult individuals of global distribution. Shape and size of the ribcage was quantified using geometric morphometrics. Our results show that the ribcage belonging to tropical individuals is smaller and slenderer compared to others living in higher latitudes, which is in line with Allen and Bergmann's rules and suggests an allometric relationship between size and shape. Although sexual dimorphism was observed in the whole sample, significant differences were only found in tropical populations. Our proposal is that, apart from potential sexual selection, avoiding heat loss might be the limiting factor for sexual dimorphism in cold-adapted populations.

Biliary Complications Post Transjugular Intrahepatic Portosystemic Shunt in a Child With Portal Vein Cavernous Transformation.

The transjugular intrahepatic portosystemic shunt is a rising interventional procedure with multiple indications and high technical success but with risks of biliary injuries, an underreported scenario. We present an 11-year-old patient with biliary injury with a leak, biloma formation, and biliary obstruction caused by the percutaneous procedure. Interventional radiology drainages addressed these complications by resolving the leak and biloma. These biliary complications in percutaneous procedures and their management are rarely reported in the medical literature, making their management not standard. We highlight drainage management and the importance of sharing it to add experience to this clinical scenario and encourage sharing cases with similar diagnoses.

[4]Rhombene: Solution-Phase Synthesis and Application for Distributed Feedback Lasers With Emission Beyond 830 nm.

Graphene-like molecules with multiple zigzag edges are emerging as promising gain materials for organic lasers. Their emission wavelengths can vary widely, ranging from visible to near-infrared (NIR), as molecular size increases. Specifically, rhombus-shaped molecular graphenes with two pairs of parallel zigzag edges, known as [n]rhombenes, are excellent candidates for NIR lasers due to their small energy gaps. However, synthesizing large-size rhombenes with emission beyond 800 nm in solution remains a significant challenge. In this study, we present a straightforward synthesis of an aryl-substituted [4]rhombene derivative, [4]RB-Ar, using a method that combines intramolecular radical-radical coupling with Bi(OTf)3-mediated cyclization of vinyl ethers. The structure of [4]RB-Ar was confirmed through X-ray crystallographic analysis. Bond length analysis and theoretical calculations indicate that aromatic sextets are predominantly localized along the molecule's long axis. Significantly, [4]RB-Ar demonstrates narrow amplified spontaneous emission at around 834 nm when dispersed in polystyrene thin films. Moreover, solution-processed distributed feedback lasers employing [4]RB-Ar as the active gain material display tunable narrow emissions in the range of 830 to 844 nm.

Multicenter external validation of prediction models for clinical outcomes after spinal fusion for lumbar degenerative disease.

BACKGROUND: Clinical prediction models (CPM), such as the SCOAP-CERTAIN tool, can be utilized to enhance decision-making for lumbar spinal fusion surgery by providing quantitative estimates of outcomes, aiding surgeons in assessing potential benefits and risks for each individual patient. External validation is crucial in CPM to assess generalizability beyond the initial dataset. This ensures performance in diverse populations, reliability and real-world applicability of the results. Therefore, we externally validated the tool for predictability of improvement in oswestry disability index (ODI), back and leg pain (BP, LP). METHODS: Prospective and retrospective data from multicenter registry was obtained. As outcome measure minimum clinically important change was chosen for ODI with ≥ 15-point and ≥ 2-point reduction for numeric rating scales (NRS) for BP and LP 12 months after lumbar fusion for degenerative disease. We externally validate this tool by calculating discrimination and calibration metrics such as intercept, slope, Brier Score, expected/observed ratio, Hosmer-Lemeshow (HL), AUC, sensitivity and specificity. RESULTS: We included 1115 patients, average age 60.8 ± 12.5 years. For 12-month ODI, area-under-the-curve (AUC) was 0.70, the calibration intercept and slope were 1.01 and 0.84, respectively. For NRS BP, AUC was 0.72, with calibration intercept of 0.97 and slope of 0.87. For NRS LP, AUC was 0.70, with calibration intercept of 0.04 and slope of 0.72. Sensitivity ranged from 0.63 to 0.96, while specificity ranged from 0.15 to 0.68. Lack of fit was found for all three models based on HL testing. CONCLUSIONS: Utilizing data from a multinational registry, we externally validate the SCOAP-CERTAIN prediction tool. The model demonstrated fair discrimination and calibration of predicted probabilities, necessitating caution in applying it in clinical practice. We suggest that future CPMs focus on predicting longer-term prognosis for this patient population, emphasizing the significance of robust calibration and thorough reporting.

A family of Cd(II) coordination polymers constructed from 6-aminopicolinate and bipyridyl co-linkers: study of their growth in paper and photoluminescence sensing of Fe3+ and Zn2+ ions.

In this work, we report on five novel coordination polymers (CPs) based on the linkage of the [Cd(6apic)2] building block [where 6apic = 6-aminopicolinate] by different bipyridine-type organic spacers, forming different coordination compounds with the following formulae: [Cd(µ-6apic)2]n (1), {[Cd(6apic)2(µ-bipy)]·H2O}n (2), {[Cd(6apic)2(µ-bpe)]·2H2O}n (3), [Cd(6apic)(µ-6apic)(µ-bpa)0.5]n (4) and {[Cd2(6apic)4(µ-tmbp)]·7H2O}n (5) [where bipy = 4,4'-bipyridine, bpe = 1,2-di(4-pyridyl)ethylene, bpa = 1,2-di(4-pyridyl)ethane (bpa) and tmbp = 1,3-di(4-pyridyl)propane]. Most of the synthesized compounds form infinite metal-organic rods through the linkage of the building block by the bipyridine-type linker, except in the case of compound 4 whose assembly forms a densely packed 3D architecture. All compounds were fully characterized and their photoluminescence properties were studied experimentally and computationally through density functional theory (DFT) calculations. All compounds display, upon UV excitation, a similar blue emission of variable intensity depending on the linker employed for the connection of the building units, among which compound 2 deserves to be highlighted for its room temperature phosphorescence (RTP) with an emission lifetime of 32 ms that extends to 79 ms at low temperature. These good photoluminescence properties, in addition to its stability in water over a wide pH range (between 2 and 10), motivated us to study compound 2 as a sensor for the detection of metal ions in water, and it showed high sensitivity to Fe3+ through a fluorescence turn-off mechanism and an unspecific turn-on response to Zn2+. Furthermore, the compound is processed as a paper-based analytical device (PAD) in which the phosphorescence emission is preserved, improving the sensing capacity toward Fe3+ ions.

Full-genome sequencing of dozens of new DNA viruses found in Spanish bat feces.

Bats are natural hosts of multiple viruses, many of which have clear zoonotic potential. The search for emerging viruses has been aided by the implementation of metagenomic tools, which have also enabled the detection of unprecedented viral diversity. Currently, this search is mainly focused on RNA viruses, which are largely over-represented in databases. To compensate for this research bias, we analyzed fecal samples from 189 Spanish bats belonging to 22 different species using viral metagenomics. This allowed us to identify 52 complete or near-complete viral genomes belonging to the families Adenoviridae, Circoviridae, Genomoviridae, Papillomaviridae, Parvoviridae, Polyomaviridae and Smacoviridae. Of these, 30 could constitute new species, doubling the number of viruses currently described in Europe. These findings open the door to a more thorough analysis of bat DNA viruses and their zoonotic potential. IMPORTANCE: Metagenomics has become a fundamental tool to characterize the global virosphere, allowing us not only to understand the existing viral diversity and its ecological implications but also to identify new and emerging viruses. RNA viruses have a higher zoonotic potential, but this risk is also present for some DNA virus families. In our study, we analyzed the DNA fraction of fecal samples from 22 Spanish bat species, identifying 52 complete or near-complete genomes of different viral families with zoonotic potential. This doubles the number of genomes currently described in Europe. Metagenomic data often produce partial genomes that can be difficult to analyze. Our work, however, has characterized a large number of complete genomes, thus facilitating their taxonomic classification and enabling different analyses to be carried out to evaluate their zoonotic potential. For example, recombination studies are relevant since this phenomenon could play a major role in cross-species transmission.

Catalytic asymmetric synthesis of 1,2-diamines.

The asymmetric catalytic synthesis of 1,2-diamines has received considerable interest, especially in the last ten years, due to their presence in biologically active compounds and their applications for the development of synthetic building blocks, chiral ligands and organocatalysts. Synthetic strategies based on C-N bond-forming reactions involve mainly (a) ring opening of aziridines and azabenzonorbornadienes, (b) hydroamination of allylic amines, (c) hydroamination of enamines and (d) diamination of olefins. In the case of C-C bond-forming reactions are included (a) the aza-Mannich reaction of imino esters, imino nitriles, azlactones, isocyano acetates, and isothiocyanates with imines, (b) the aza-Henry reaction of nitroalkanes with imines, (c) imine-imine coupling reactions, and (d) reductive coupling of enamines with imines, and (e) [3+2] cycloaddition with imines. C-H bond forming reactions include hydrogenation of CN bonds and C-H amination reactions. Other catalytic methods include desymmetrization reactions of meso-diamines.